JPS63178124A - Amine curing agent composition - Google Patents

Abstract

PURPOSE:To obtain an amine curing agent which, when mixed with an epoxy resin, can give a film excellent in chemical resistance and boiling water resistance, by using a reaction product among a polyepoxy compound, a polyamine and a mono(meth)acrylic compound as a component. CONSTITUTION:An amine curing agent composition containing a mixture of product of formulas VII and VIII [wherein U is a residue of an amine (ii) of, e.g., formula III and V is a residue of a compound (iii) of formula V], obtained by reacting a polyepoxy compound (i) of, e.g., formula II (wherein R1-R4 are each H, a halogen or the like), having at least three epoxy groups, at least one of which is a glycidylamino group of formula I, in the molecule with an aliphatic polyamine or the like (ii) comprising a polyalkylenepolyamine or polyetherpolyamine of formula III (wherein A is a group of formula IV, a>=1 and b>=1) and a mono(meth)acrylic compound (iii) of formula V (wherein T is H or the like and E is a group of formula VI or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful amine-based curing agent composition, which provides a film having excellent chemical resistance and boiling water resistance when mixed with an epoxy resin. A composition is provided.

As a so-called heavy-duty anticorrosive paint for areas exposed to harsh conditions such as ships, bridges, and offshore structures,
Amine-curing epoxy resin paints are often used, but among them, paints for tank interiors that require particularly high chemical resistance simply have excellent painting workability, ability to prevent cargo from becoming contaminated, and chemical resistance. Is the amine-curing Nixy resin compatible with inorganic or organic sink-rich resins? It is only used as a primer.

By the way, the amine-based curing agent for this food uses amine adduct, which has excellent chemical resistance and low toxicity.It also has excellent boiling water resistance and product resistance, and has even improved chemical resistance. What is desired is something that gives

Under these circumstances, as a means of improving performance, a method for producing polyfunctional amine-based curing agents was proposed in JP-A-58, which aims to increase the degree of branching of the curing agent itself and increase the number of active hydrogen per molecule.
Although it is disclosed in Publication No. -210050,
Although it is true that using the hardening agent obtained by this manufacturing method improves chemical resistance and boiling water resistance compared to conventional ones, the polarity of the hardening agent is different from that of the main resin, which is the hardening agent. The strength is also quite high and the difference in solids is large, so there are difficulties in compatibility, and as a result, the coating film undergoes microscopic phase separation, making it difficult to demonstrate its performance, especially when drying at room temperature. However, there are drawbacks such as easy repellency.

Furthermore, the coating film using the curing agent obtained by this production method still has many practical problems, such as cracking and cracking when subjected to a relatively mild impact.

However, in view of these actual circumstances, the inventors of the present invention have found excellent compatibility with the main resin resin and impact resistance, as well as chemical resistance, solvent resistance, fatty acid resistance, condensation resistance, product resistance, and resistance. As a result of intensive research to obtain a polyfunctional amine compound that is particularly useful as an amine epoxy resin curing agent that has excellent boiling water resistance and adhesion, the present invention has been completed.

That is, the present invention uses as essential components a polyethylene compound (a), an aliphatic, alicyclic and/or aromatic polyamine (b), and a mono(meth)acrylic compound (C).
A product obtained by the reaction with a specific glycidylamino compound (, ) having three or more epoxy groups in one molecule and at least one of which is represented by the formula a compound having a group,
In particular, compounds represented by the general formula NlN5N', N'-tetraglycidyl-m-xylene diamine, and general compounds represented by N,N,N',N'-tetraglycidylbis(aminomethyl)cyclohexane. A compound represented by the general formula represented by the formula, N,N-diglycidyl-aminophenyl-glycidyl ether, a general formula represented by N,N-diglycidyl-aminophenyl-glycidyl ether Compounds represented by the general formula represented by N, NeN', N'-tetraglycidyl-diamino-diphenylmethane, and N, NIN', N'-
The present invention provides compounds represented by the general formula represented by tetraglycidyl-diamino-cyclohexylmethane.

The present shell composition having such a structure uses the polyepoxy compound (a) having a tertiary amine group as an epoxy resin curing catalyst as the e-component compound, and the various compounds (c) also have a molecular structure. The overall polarity is lower than that of a polyfunctional amine curing agent obtained by reacting only the compound (,) and the compound (b) because of the introduction of the compound into the curing agent. In addition, flexibility has also been improved, and these effects result in excellent compatibility with the main resin resin, which in turn provides excellent coating film curing properties, as well as chemical resistance, product resistance, and boiling water resistance. It can also serve as an amine-based curing agent that has excellent anti-corrosion properties such as adhesion.

Here, the polyepoxy compound (,) is one obtained by reacting an amine group-containing compound' such as Φsilenediamine, aminephenol or cyamino diphenylmethane, a primary conductor thereof, or a hydrogenated product thereof with epichlorohydrin. Having 3 or more epoxy groups in one molecule, and at least one of them
It is a synonym for a compound or resin in which each is a glycidylamino group represented by the formula, and among others, N, N,
N',N'-tetraglycidyl-m-xylene diamine is preferred.

In addition, as the polyamine (b), all those normally used as raw materials for amine curing agents can be used, but among them, the most representative one is ethylenediamine represented by the general formula %. /, diethylenetriamine,
Especially polyalkylene polyamines such as triethylene diamine, tetraethylene pentamine or pentaethylene hexamino? Aliphatic polyamines such as polyether polyamines, including diethylene polyamines; phenylene diamine, tolylene diamine,
Aromatic diamines such as xylene diamine or diaminodiphenylmethane; alicyclic diamines such as inphorone diamine, hydrogenated m-xylene diamine or hydrogenated diaminodiphenylmethane, or each of these low molecular weight polyamines ( b) includes I-lyamidoamines which are reacted with dimer acid or monomer acid. These may be used alone or in combination of two or more.

Next, as the above-mentioned compound (c), acrylonitrile or methacrylonitrile, acrylic acid, methacrylic acid, ethyl acrylate, which is typically represented by the general formula,
Propyl acrylate, n-butyl acrylate, 2-
Various acrylic esters such as ethylhexyl acrylate or benzyl acrylate, various methacrylic esters such as methyl methacrylate, tart-butyl methacrylate or lauryl methacrylate, β
- Various (meth)acrylic acid hydroxyesters such as hydroxyacrylate or β-hydroxymethacrylate, or acrylamide or methacrylamide and derivatives thereof, and these may be used alone or in combination of two or more types. You may.

Various mono(meth)acrylic compounds (C) that appear to have subsided
In addition, there is no problem in using the following monoepoxy compounds and monoamine compounds.

As such monoepoxy compounds, any commercially available compounds can be used, but representative ones include olefin oxides such as alkylene oxide or styrene oxide; alkyl glycidyl ethers and allyl glycidyl ethers. Various glycidyl ethers such as hafeel glycidyl ether or derivatives thereof, alkoxy I realkylene ether or glycidyl ether; or various glycidyl esters such as benzoic acid glycidyl ester or no-satic acid glycidyl ester; Reeds, these can be used alone,
Two or more types may be used in combination.

On the other hand, as the monoamine compound, all commercially available compounds can be used, but typical examples include ethylamine, propylamine, butylamine, cyclohexylamine, benzylamine, ethanolamine, and methoxypropylamine. aliphatic amines such as biridine, bicolin, morpholine, or ethyleneimine; or aromatic amines such as aniline; or derivatives thereof, and these may be used alone or in combination of two types. The above may be used in combination.

The above-mentioned compound (,) is reacted with the polyepoxy compound (in a range of 0.2 to 6 molar equivalents, particularly in a range of 0.5 to 4.0 molar equivalents, relative to 1 molar equivalent of the phantom). is preferable.

The composition of the present invention is obtained by reacting the above-mentioned raw materials (1), (b) and (,). When using an epoxy compound, it is preferable for synthesis to first perform an addition reaction between compound (,) and compound (b), and then react with compound (c) and a monoepoxy compound. , such a method is particularly recommended. The reasons are (a), (b), (e)
When reacting simultaneously, or when reacting (b) and (, ) first, these (a) and (b)
The three-component compounds (C) and (C) may not be incorporated into the same molecule, and if such unfavorable reaction products or reaction mixtures are used, it will be advantageous to meet the objectives of the present invention, and in particular, This is because it may lead to a decrease in corrosion resistance.

In order to prepare the polyfunctional amine compounds which are the reaction products of (a), (b) and (c), a commonly used method can be used as is.
It is common to choose a condition of ~5 hours.

The reaction product thus obtained, a polyfunctional amine compound, is particularly applied as a curing agent for room-temperature curable epoxy resins, but the product may also be used as it is, and is usually classified as a solvent for epoxy resins. It may be used after being diluted with various solvents or diluents.

In this way, the composition of the present invention has the above-mentioned (a) and (b)
) and (e) as essential components, but depending on the application, the composition of the present invention may also contain catalysts, fillers, pigments, or various other additives. It can be included as

The composition of the present invention is mainly used as a curing agent for coating resins, but can also be used as a curing agent for adhesives, molding materials, laminated materials, lining materials, etc.

In particular, when the composition of the present invention is used as a curing agent for paint resin, it is possible to provide a coating film with excellent gloss and adhesion without plumping or brushing, and can be applied to the inner surface of the rank of a product carrier ship. It exhibits excellent chemical resistance, product resistance, boiling water resistance, and adhesion in the field of heavy-duty anticorrosion paints, and exhibits round physical properties.

At that time, depending on the application, it can be used in combination with other curing agents for epoxy resins, and it is of course possible to add catalysts, fillers, pigments, etc. as necessary each time. .

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and parts are based on weight unless otherwise specified.

Example 1 412 parts of diethylenetriamine and 100 parts of triol were charged into a four-sided flask of 1j, and the temperature was raised to 80°C, and N, N, N', with an epoxy equivalent of 102,
20 of N'-tetraglycidyl-m-xylene diamine
4 parts were charged in portions over about 30 minutes, reacted at 120°C for 1 hour, heated to 180°C, removed toluene and excess diethylenetriamine under reduced pressure, and then cooled to 60°C. Then, the reaction was carried out in the same manner as in Example 1 except that 26":5 parts of acrylonitrile was added in place of 9 instead of phenyl glycidyl ether, and then 124 parts of toluene and 62 parts of n-butanol were added. A clear reaction mixture solution containing 70% NY was obtained.

The reaction mixture thus obtained was a mixture mainly consisting of a compound having the following structural formula.

... [Kari-■] and H ... [Kari-■] Example 2 Instead of N, N, N', N'-tetraglycidyl-m-xylene diamine, NtN, N', N/- 20 of tetraglycidyl-bis(aminomethyl)cyclohexane
A transparent reaction mixture solution containing 70% W was obtained in the same manner as in Example 1, except that 7 parts were used.

However, the amounts of toluene and n-butanol to be added were 125 parts and 63 parts, respectively.

The resulting mixture was mainly composed of a compound represented by the following structural formula.

...[■-■] Example 3 NININ', 138 parts t'' of N,N-diglycidyl-m-aminophenylglycidyl ether was used in place of N'-tetraglycidyl-m-xylene diamine,
Example 1 except that 50 parts of methyl methacrylate was used instead of acrylonitrile.
A transparent reaction mixture solution having NY of 70 was obtained in the same manner as above.

However, the amounts of toluene and n-butanol to be added were 113 parts and 65 parts, respectively.

The reaction mixture obtained here consisted mainly of a compound represented by the following structural formula.

H .
A clear reaction mixture solution containing 70 mushrooms was prepared in the same manner as in Example 1, except that 281 parts of diglycidyl-4-aminocyclohexyl glycidyl ether was used and the amount of acrylonitrile was changed to 53 parts. Obtained.

However, the amounts of toluene and n-butanol to be added were 154 parts and 77 parts, respectively.

The reaction mixture obtained here was a mixture mainly consisting of a compound represented by the following structural formula.

...(:XV-1) and (XV-211 Example 5 NIP with an epoxy equivalent of 106 instead of NtNIN'IN'-tetraglycidyl-m-xylene diamine
'LN', using 212 parts of N'-tetraglycidyl-diaminodiphenylmethane, using 425 parts of inphorondian instead of diethylenetriamine, and
A transparent reaction mixture solution containing 70 mushrooms was obtained in the same manner as in Example 1, except that 71 parts of n-butyl methacrylate was used instead of acrylonitrile.

However, as the solvents to be added, 202 parts of toluene and 101 parts of n-butanol were used.

The mixture thus obtained was mainly composed of a compound represented by the following structural formula.

Example 6 N#N, N', N'-tetragucidyl-m-xylene diamine was replaced with N where the engineering number was 109,
Using 58 parts of N,N',N'-tetraglycidyl-diaminodicyclohexylmethane, replacing diethylenetriamine with 386 parts of diaminodiphenylmethane, and replacing acrylonitrile with 20 parts of methyl methacrylate. A transparent reaction mixture solution with an NV of 70% was obtained in the same manner as in Example 1, except that the reaction mixture was changed to .

However, the amounts of toluene and n-butanol to be added were changed to 140 parts and 70 parts, respectively.

The mixture thus obtained consisted entirely of compounds represented by the following structural formula.

Example 7 A transparent reaction mixture containing 70% W was prepared by repeating the same procedure as in Example 2, except that 65 parts of β-hydroxyethyl methacrylate was used in place of the nitrile. A solution was obtained.

However, as the solvents to be added, 138 parts of toluene and 69 parts of n-butanol were used.

The reaction mixture obtained here consisted mainly of a compound represented by the following structural formula.

H Ward H ... [Expletive-1] Example 8 A transparent reaction mixture solution containing 70 parts of mushrooms was prepared in the same manner as in Example 4, except that 84 parts of cyclohexyl methacrylate was used instead of acrylonitrile. I got it.

However, the amounts of toluene and n-butanol to be added were 108 parts and 54 parts, respectively.

The mixture obtained here is mainly composed of a compound represented by the following structural formula (9).

H ・-(m-1) and H ■ Example 9 Except for using 88.5 parts of benzyl methacrylate instead of n-butyl methacrylate,
A transparent reaction mixture solution containing 70 inches of W was obtained in the same manner as in Example 5.

However, the amounts of toluene and n-butanol to be added were 183 parts and 92 parts, respectively.

The resulting mixture was mainly composed of a compound represented by the following structural formula.

Example 10 3 of 1 acrylamide in place of methyl methacrylate
A transparent reaction mixture solution with 701 lines was obtained in the same manner as in Example 6, except that 5.5 parts or more was used.

However, as the solvents to be added, 186 parts of toluene and 93 parts of n-butanol were used.

In particular, the reaction mixture obtained was a mixture mainly consisting of a compound represented by the following structural formula.

Comparative Example 1 380 parts of [Evicron 1050JC epoxy resin manufactured by Dainippon Ink & Chemicals ■; epoxy equivalent = 475], 120 parts of diethylenetriamine, and 160 parts of xylene were reacted at 120°C for 1 hour, and then heated to 180°C. The mixture was allowed to warm up to 1 temperature, and the xylene and excess diethylenetriamine were removed under reduced pressure.

To this was then added 250 parts of xylene and 250 parts of n-butanol to obtain a clear solution of the amino adduct with a formula of 50.2%.

Comparative Example 2 Example 1 except that the amount of solvent added after removing toluene and excess diethylenetriamine was changed to 118 parts of toluene and 58 parts of n-butanol.
In the same manner as above, a transparent solution with V of 70 was obtained, which was a mixture mainly consisting of a compound represented by the following structural formula.

...(U-11) Each of the reaction mixtures obtained above was separately treated with "Epicron 10
50-75XJ [: Dainippon Ink & Chemicals ■Epoxy resin] is blended so that the epoxy group and active hydrogen are equivalent, and then xylene and n-butanol (1:1) are added.
-141 ratio) was diluted with a mixed solvent such that the solid content of the blended resin was 60%, and the mixture was stirred.

Next, each of the clear paints thus obtained was individually applied to a sandblasted steel plate using an airless sprayer so that the dry paint film had a thickness of 125 μm.

For each of these coatings, coating film physical properties and chemical immersion tests were conducted. The results are summarized in Table 1 and show that the composition of the present invention has better boiling water resistance, chemical resistance, solvent resistance, etc. compared to the conventional amine adduct curing agent (Comparative Example 1). It is known that it exhibits excellent anticorrosion performance. In addition, the anticorrosive performance is superior to that of the conventional polyfunctional curing agent (Comparative Example 2), and a remarkable improvement in impact resistance is also observed.

Claims (1)

[Scope of Claims] One molecule has three or more epoxy groups, and at least one of them is a glycidylamino group represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] , General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [However, R_1, R_2, R_3, and R_4 in the formula
each represents a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. ] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [III] [However, R_1, R_2, R_3 and R_4 in the formula each represent a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. ] General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [IV] [However, R_1, R_2, R_3 and R_4 in the formula each represent a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. ] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [V] [However, R_1, R_2, R_3, and R_4 in the formula each represent a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VI] [However, R_1, R_2, R_3, R_4, R_ in the formula
5, R_6, R_7 and R_8 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group. ] Or general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VII] [However, R_1, R_2, R_3, R_4, R_ in the formula
5, R_6, R_7 and R_8 each represent a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group. ] A polyepoxy compound (a) represented by the general formula H_2N-(A)-_aNH_2 [VIII] [However, A in the formula is -C_bH_2_bNH- (However,
It is assumed that b is an integer of 1 or more. ), or -CHR-CH_2-O-CHR-CH_2-NH-(
However, R represents a methyl group. ), and a is an integer of 1 or more. ] Aliphatic polyamines such as polyalkylene polyamines or polyether polyamines; general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [IX] [However, c, d, e, f, g and h in the formula are Both are 0 or 1, but c, d, e, f, g, and h never take the same number at the same time, and when h is 1, d, e, f, and g both take 0. On the other hand, when h is 0, either c and d, e and f both take 1 and only g takes 0, or c
Either e and g take 1 and d and f both take 0, or c and e both take 1 and only d and f take 0. shall be taken as a thing. ] Aromatic diamines such as phenylene diamine, tolylene diamine, xylene diamine, or diaminodiphenylmethane; and/or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [X] [However, i, j in the formula , k, l, p, q and r are each 0 or 1, but i and j and k and l and p and q and r never take the same number at the same time, and r is 1.
, then i, j, k, l, p and q are all 0
On the other hand, when r is 0, either j, k, and l both take 0 and i, p, and q both take 1, or j, k, l, p, and q It is assumed that either both are 1 and only i is 0. ] Alicyclic diamines (b) represented by isophorone diamine, hydrogenated m-xylene diamine or hydrogenated diaminodiphenylmethane, and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [X I ] [However, , T in the formula represents a hydrogen atom or a methyl group, and E is C_bH-_2_b_+_1COO- (however, b is as described above), HO-C_bH-_2_b_+_1COO- (however, b
is as mentioned above. ), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, s is as above.), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, s is as above.), -CONH_2 or -CN. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [XII- I
] Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...[XII-II] [However, R_1, R_2, R_3 and R_4 in each formula
is as mentioned above, and U is [VIII], [IX] and [X
] The residue of each amine (b) represented by the formula is
I] represents the residue of each compound (e) represented by the formula. ] A mixture of each product typically represented by the general formula ▲ mathematical formula,
There are chemical formulas, tables, etc.▼...[XIII-I] Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[XIII-II
] [However, R_1, R_2, R_3, R_4, U in each formula
and V are as described above. ] A mixture of each product typically represented by the general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼...[XIV-I] or ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[XIV-II] [However, R_1, R_2, R_3, R_4, U in each formula
and V are as described above. ] A mixture of each product typically represented by the general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼...[XV-I] or ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[XV-II] [However, R_1, R_2, R_3, R_4, U in each formula
and V are as described above. ] A mixture of each product typically represented by the general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼... [XVI] [However, R_1, R_2, R_3, R_4, R in each formula
It is assumed that _5, R_6, R_7, R_8, U and V are as described above. [XVII] [However, R_1, R_2, R_3, R_4, R in each formula]
It is assumed that _5, R_6, R_7, R_8, U and V appear as described above. ] An amine curing agent composition comprising as an essential component a mixture of the products typically shown below.